US5009798A - Low fluid loss heavy brines containing hydroxyethyl cellulose - Google Patents
Low fluid loss heavy brines containing hydroxyethyl cellulose Download PDFInfo
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- US5009798A US5009798A US07/336,592 US33659289A US5009798A US 5009798 A US5009798 A US 5009798A US 33659289 A US33659289 A US 33659289A US 5009798 A US5009798 A US 5009798A
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- United States
- Prior art keywords
- hydroxyethyl cellulose
- brine
- concentration
- zinc bromide
- fluid loss
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- 229920000663 Hydroxyethyl cellulose Polymers 0.000 title claims abstract description 70
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 title claims abstract description 70
- 239000004354 Hydroxyethyl cellulose Substances 0.000 title claims abstract description 66
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims abstract description 80
- 229940102001 zinc bromide Drugs 0.000 claims abstract description 40
- 239000012267 brine Substances 0.000 claims abstract description 39
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 39
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000001110 calcium chloride Substances 0.000 claims abstract description 23
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 23
- 229910001622 calcium bromide Inorganic materials 0.000 claims abstract description 20
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 230000003247 decreasing effect Effects 0.000 claims description 5
- WAYQYYCPNLDKMS-UHFFFAOYSA-L calcium;zinc;bromide;chloride Chemical compound [Cl-].[Ca+2].[Zn+2].[Br-] WAYQYYCPNLDKMS-UHFFFAOYSA-L 0.000 claims 1
- 239000008186 active pharmaceutical agent Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- -1 zinc bromide Chemical class 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920001477 hydrophilic polymer Polymers 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YAXKTBLXMTYWDQ-UHFFFAOYSA-N 1,2,3-butanetriol Chemical compound CC(O)C(O)CO YAXKTBLXMTYWDQ-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- AALKGALVYCZETF-UHFFFAOYSA-N pentane-1,2,3-triol Chemical compound CCC(O)C(O)CO AALKGALVYCZETF-UHFFFAOYSA-N 0.000 description 1
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
- C09K8/08—Clay-free compositions containing natural organic compounds, e.g. polysaccharides, or derivatives thereof
- C09K8/10—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/18—Bridging agents, i.e. particles for temporarily filling the pores of a formation; Graded salts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/926—Packer fluid
Definitions
- the present invention relates to heavy brine solutions containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide, and, in particular, to such brines having a low fluid loss containing hydroxyethyl cellulose.
- the high density clear brines are used extensively: as completion fluids to minimize plugging of perforation tunnels, to protect formation permeability and to minimize mechanical problems; as workover fluids, for the same reasons; as packer fluids, to allow easy movement and retrieval of the packer; for underreaming, gravel-pack and sand consolidation applications; as kill fluid or ballast fluid; for wire-line work; and as drilling fluids.
- Clear brines having a density of 14.2 pounds per gallon (ppg) or lower are generally formulated to contain sodium chloride, sodium bromide, potassium chloride, calcium chloride, calcium bromide, or mixtures of these salts.
- Clear brines having a density up to about 15.1 ppg can be formulated with calcium chloride and calcium bromide; however, if the brine must have a low crystallization temperature, then clear brines in this density range are generally formulated to contain a soluble zinc salt.
- Zinc bromide is preferred because brines containing it are less corrosive than brines containing zinc chloride.
- Clear brines having a density greater than about 15.1 ppg are formulated to contain zinc bromide.
- HEC hydroxyethyl cellulose
- xanthan gum polymers are compatible with the fluids which do not contain zinc salts.
- the hydration of the viscosifiers is significantly slower.
- HEC is generally considered as unsatisfactory for use in fluids containing zinc salts.
- HEC will function as a fluid loss additive in certain heavy brines in which HEC does not function efficiently as a viscosifier.
- These heavy brines contain either:
- an object of this invention to provide certain heavy brine solutions containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide, and a fluid loss reducing amount of hydroxyethyl cellulose.
- Another object of this invention is to provide heavy brine solutions having a density in the range from about 14.2 to about 16.0 ppg containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide, and a fluid loss reducing amount of hydroxyethyl cellulose.
- Still another object of this invention is to provide a method of decreasing the fluid loss of heavy brines having a density in the range from about 14.2 to about 16.0 ppg containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide.
- the heavy brines for use in the present invention contain zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide.
- the concentration of zinc bromide must be in the range from about 16% to about 20% by weight.
- concentration of zinc bromide is ⁇ 18% and the concentration of calcium chloride is ⁇ 5(X-17)% where X is the % of zinc bromide.
- the brine must contain greater than 20% by weight zinc bromide and a concentration of calcium chloride of at least (2X-33)% by weight, where X is the % of zinc bromide.
- the preferred brines have a density in the range from about 14.2 to about 16.0 ppg.
- heavy brines are prepared by mixing together various standard commercially available brines, as follows: calcium chloride brines having a density in the range from about 11.0 to about 11.6 ppg; calcium bromide brine having a density of 14.2 ppg; and a calcium bromide/zinc bromide solution having a density of 19.2 ppg containing about 20% calcium bromide and about 57% zinc bromide.
- Solid calcium chloride and solid calcium bromide are also used in conjunction with these brines to prepare the heavy brines for use in this invention. However, it is preferred to utilize only liquid solutions to formulate the brines in the practice of this invention. Standard brine mixing/preparation tables are available from the various manufacturers and suppliers of these commercially available brines.
- HEC polymers which are useful as fluid loss control agents in the present invention are solid, particulate materials which are water soluble or water dispersible gums and which upon solution or dispersion in an aqueous medium increase the viscosity of the system.
- HEC polymers are generally high yield, water soluble, non-ionic materials produced by treating cellulose with sodium hydroxide followed by reaction with ethylene oxide.
- Each anhydroglucose unit in the cellulose molecule has three reactive hydroxy groups.
- the average number of moles of the ethylene oxide that becomes attached to each anhydroglucose unit in cellulose is called moles of substituent combined.
- the average number of hydroxyls of each anhydroglucose unit which is reacted with ethylene oxide is called the degree of substitution.
- HEC and other hydrophilic polymers can be activated such that the polymers will viscosify heavy brines at ambient temperatures.
- Activated HEC compositions, and methods for activating HEC are disclosed in the following listed co-pending patent applications incorporated herein by reference for all purposes: Ser. No. 119,805 filed Feb. 8, 1980, now U.S. Pat. No. 4,330,414, entitled Dispersible Hydrophilic Polymer Compositions; and Ser. No. 146,286 filed May 5, 1980, now U.S. Pat. No. 4,392,964, entitled Compositions and Method for Thickening Aqueous Brines. Methods of activating other hydrophilic polymers are disclosed in co-pending patent application Ser. No. 196,367 filed Oct. 14, 1980, now U.S. Pat. No. 4,427,556, entitled Dispersible Hydrophilic Polymer Compositions, incorporated herein by reference for all purposes.
- Activated HEC compositions comprise:
- HEC a solvating agent comprising a water miscible, polar organic liquid which when uniformly mixed with HEC in a weight ratio of HEC to solvating agent of 1:2 produces a mixture with substantially no free liquid solvating agent present after remaining quiescent for one week at ambient temperature in a sealed container, and a diluting agent comprising an organic liquid which is not a solvating agent;
- HEC HEC
- aqueous liquid a water soluble polar organic liquid which when uniformly mixed with HEC in a weight ratio of HEC to polar organic liquid of 1:2 produces a mixture with free liquid present after remaining quiescent for one week at ambient temperature in a sealed container.
- the aqueous liquid has a pH greater than 7.0.
- Non-limiting but preferred solvating agents include: aliphatic glycols containing from 2 to 5 carbon atoms such as ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,3-pentanediol and the like; alkylene triols containing from 2 to 6 carbon atoms such as glycerol, 1,2,3-butane-triol, 1,2,3-pentanetriol, and the like; amides containing from 1 to 4 carbon atoms such as formamide, acetamide, dimethyl formamide, and the like; and the mixtures of the various above compounds.
- the diluting agent in general, will be any liquid organic compound or material which is not a solvating agent.
- the diluting agents are liquids which do not appreciably swell the HEC polymers, i.e. they do not produce semisolid or viscous mixtures which have no free liquid present after the one week solvation period described in the above test for determining solvating agents.
- Non-limiting examples of diluting agents include liquid aliphatic and aromatic hydrocarbons containing from 5 to 10 carbon atoms; kerosene, diesel oil, isopropanol, alkylene glycol ethers, vegetable oils, etc.
- organic liquids which are water soluble or miscible most preferably alkanols having at least 3 carbon atoms, ethylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and the like.
- the diluting agent will maintain the polymeric composition in a liquid, pourable state at a temperature of about 20° C. It will be understood, however, that lesser amounts of diluting agent can be used if desired and that the ultimate amount of diluting agent employed will depend upon the type of shear which is available to disperse the thickener.
- desirable thickeners which are pourable liquids, can be produced from compositions containing from about 10 to about 25% by weight HEC polymer, from about 2 to about 70% by weight diluting agent, and from about 5 to about 88% solvating agent.
- HEC has been added to heavy brines to increase the viscosity of the brine such that the rate of loss of the brine to the formation contacted by the brine is reduced.
- hydroxyethyl cellulose provides poor fluid loss control in those brines in which the HEC is fully hydrated. See for example co-pending patent application Ser. No. 161,444 filed June 20, 1980, entitled Thickened Heavy Brines, incorporated herein by reference.
- HEC functions as an excellent fluid loss control additive in certain heavy brines in which the HEC is a very inefficient viscosifier.
- the HEC containing brines of this invention are cloudy or opaque as compared to the clear brines obtained when the HEC is completely, or nearly completely, hydrated. Apparently the HEC is not completely solubilized in these brines and thus at least a portion of the HEC is available to act as a bridging agent to decrease the fluid loss of these brines.
- the HEC be activated such that the HEC will hydrate in these heavy brines at ambient temperature.
- the concentration of HEC need only be sufficient to reduce the fluid loss of the brine.
- the concentration of HEC will be from about 0.25 to about 5.0 ppb, more preferably, from about 0.25 to about 3.0 ppb.
- Still another embodiment of this invention provides a method of decreasing the fluid loss of heavy brines containing zinc bromide, calcium chloride, and calcium bromide, which comprises formulating the brine to contain greater than 20% zinc bromide and a concentration of calcium chloride of at least (2X-33)% by weight, where X is the % of zinc bromide, and mixing with the brine a fluid loss reducing amount of HEC, as disclosed hereinbefore.
- Heavy brines having the compositions listed in Table 1 were prepared by mixing together the indicated amounts of the following materials: a 19.2 ppg calcium bromide/zinc bromide solution containing 20% calcium bromide and 57% zinc bromide; a 14.2 ppg calcium bromide solution containing 53% calcium bromide; an 11.6 ppg calcium chloride solution containing 37.6% calcium chloride; and calcium chloride pellets containing 95% calcium chloride.
- NATROSOL 250 HHR hydroxyethyl cellulose After cooling to room temperature, there were added either: 3 ppb of NATROSOL 250 HHR hydroxyethyl cellulose; or 3 ppb of activated NATROSOL 250 HHR (i.e., 15 ppb of a composition containing 20% HEC, 25% glycerin, 54.6% isopropanol, and 0.4% CAB-O-SIL M5). Thereafter, the heavy brines were rolled 16 hours at room temperature and the API RP 13B rheology and fluid loss obtained. The heavy brines were then rolled 16 hours at 150oF, cooled at room temperature, and the API RP 13B data again obtained. The data obtained are given in Table 2.
- the data indicate that heavy brines containing HEC can be formulated to exhibit a very low API fluid loss provided the % zinc bromide in the brine is in the range from about 16% to about 20% by weight, or the % zinc bromide is greater than 20% and the calcium chloride is greater than (2X-33)% where X is the % of zinc bromide in the brine.
- the % zinc bromide is in the range from about 18% to about 20% and the % calcium chloride is less than about 5(X-17)%.
- the HEC solublizes to such an extent that appreciable viscosity is imparted to the heavy brine.
- the data also indicate that it is preferable to omit any solid calcium chloride from the heavy brine.
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Disclosed are heavy brine compositions containing zinc bromide and one or more soluble salts selected from the group consisting of calcium chloride and calcium bromide, preferably having a density in the range from about 14.2 to about 16.0 pounds per gallon, which have a low API fluid loss. Also disclosed is a method of formulating certain heavy brines in which hydroxyethyl cellulose functions as a fluid loss additive.
Description
This is a continuation of co-pending U.S. application Ser. No. 07/080,203 filed on July 29, 1987, now abandoned, which, in turn, in a continuation of U.S. application Ser. No. 06/357,308, filed Mar. 11, 1982, now abandoned, which is a continuation-in-part of U.S. application Ser. No. 06/161,444 filed June 20, 1980, now U.S. Pat. No. 4,420,406.
The present invention relates to heavy brine solutions containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide, and, in particular, to such brines having a low fluid loss containing hydroxyethyl cellulose.
In recent years, the practical operating range of clear brines for use in the oil and gas industry has been significantly extended by utilizing soluble zinc salts, particularly zinc bromide, so that the advantages of clear brines can now be obtained with fluids having densities as high as 19.2 pounds per gallon at ambient temperatures and pressures.
The high density clear brines are used extensively: as completion fluids to minimize plugging of perforation tunnels, to protect formation permeability and to minimize mechanical problems; as workover fluids, for the same reasons; as packer fluids, to allow easy movement and retrieval of the packer; for underreaming, gravel-pack and sand consolidation applications; as kill fluid or ballast fluid; for wire-line work; and as drilling fluids.
Clear brines having a density of 14.2 pounds per gallon (ppg) or lower are generally formulated to contain sodium chloride, sodium bromide, potassium chloride, calcium chloride, calcium bromide, or mixtures of these salts. Clear brines having a density up to about 15.1 ppg can be formulated with calcium chloride and calcium bromide; however, if the brine must have a low crystallization temperature, then clear brines in this density range are generally formulated to contain a soluble zinc salt. Zinc bromide is preferred because brines containing it are less corrosive than brines containing zinc chloride. Clear brines having a density greater than about 15.1 ppg are formulated to contain zinc bromide.
Generally, hydroxyethyl cellulose (HEC) and xanthan gum polymers are compatible with the fluids which do not contain zinc salts. However, at the higher densities, the hydration of the viscosifiers is significantly slower. HEC is generally considered as unsatisfactory for use in fluids containing zinc salts.
We have now found that HEC will function as a fluid loss additive in certain heavy brines in which HEC does not function efficiently as a viscosifier. These heavy brines contain either:
(1) from about 16% to about 20% by weight zinc bromide; or
(2) greater than 20% zinc bromide and a concentration of calcium chloride of at least (2X-33)% by weight, were X=% zinc bromide.
It is, therefore, an object of this invention to provide certain heavy brine solutions containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide, and a fluid loss reducing amount of hydroxyethyl cellulose.
Another object of this invention is to provide heavy brine solutions having a density in the range from about 14.2 to about 16.0 ppg containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide, and a fluid loss reducing amount of hydroxyethyl cellulose.
Still another object of this invention is to provide a method of decreasing the fluid loss of heavy brines having a density in the range from about 14.2 to about 16.0 ppg containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide.
The heavy brines for use in the present invention contain zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide.
In one embodiment of the invention, the concentration of zinc bromide must be in the range from about 16% to about 20% by weight. Preferably the concentration of zinc bromide is <18% and the concentration of calcium chloride is <5(X-17)% where X is the % of zinc bromide.
In another embodiment of the invention, the brine must contain greater than 20% by weight zinc bromide and a concentration of calcium chloride of at least (2X-33)% by weight, where X is the % of zinc bromide.
The preferred brines have a density in the range from about 14.2 to about 16.0 ppg.
Generally, heavy brines are prepared by mixing together various standard commercially available brines, as follows: calcium chloride brines having a density in the range from about 11.0 to about 11.6 ppg; calcium bromide brine having a density of 14.2 ppg; and a calcium bromide/zinc bromide solution having a density of 19.2 ppg containing about 20% calcium bromide and about 57% zinc bromide. Solid calcium chloride and solid calcium bromide are also used in conjunction with these brines to prepare the heavy brines for use in this invention. However, it is preferred to utilize only liquid solutions to formulate the brines in the practice of this invention. Standard brine mixing/preparation tables are available from the various manufacturers and suppliers of these commercially available brines.
The HEC polymers which are useful as fluid loss control agents in the present invention are solid, particulate materials which are water soluble or water dispersible gums and which upon solution or dispersion in an aqueous medium increase the viscosity of the system. HEC polymers are generally high yield, water soluble, non-ionic materials produced by treating cellulose with sodium hydroxide followed by reaction with ethylene oxide. Each anhydroglucose unit in the cellulose molecule has three reactive hydroxy groups. The average number of moles of the ethylene oxide that becomes attached to each anhydroglucose unit in cellulose is called moles of substituent combined. The average number of hydroxyls of each anhydroglucose unit which is reacted with ethylene oxide is called the degree of substitution. In general, it is preferable to use HEC polymers having a mole substitution greater than 1.
Usually, upon the addition of dry, powdered hydrophilic polymers, such as HEC, to water, the polymer particles undergo hydration preventing the interior of the particle from readily hydrating, solvating or otherwise dispersing in the aqueous medium. Accordingly, high shear, long mixing times and/or elevated temperatures must be applied in order to obtain a homogeneous system.
We have found that HEC and other hydrophilic polymers can be activated such that the polymers will viscosify heavy brines at ambient temperatures. Activated HEC compositions, and methods for activating HEC, are disclosed in the following listed co-pending patent applications incorporated herein by reference for all purposes: Ser. No. 119,805 filed Feb. 8, 1980, now U.S. Pat. No. 4,330,414, entitled Dispersible Hydrophilic Polymer Compositions; and Ser. No. 146,286 filed May 5, 1980, now U.S. Pat. No. 4,392,964, entitled Compositions and Method for Thickening Aqueous Brines. Methods of activating other hydrophilic polymers are disclosed in co-pending patent application Ser. No. 196,367 filed Oct. 14, 1980, now U.S. Pat. No. 4,427,556, entitled Dispersible Hydrophilic Polymer Compositions, incorporated herein by reference for all purposes.
Activated HEC compositions comprise:
(1) HEC, a solvating agent comprising a water miscible, polar organic liquid which when uniformly mixed with HEC in a weight ratio of HEC to solvating agent of 1:2 produces a mixture with substantially no free liquid solvating agent present after remaining quiescent for one week at ambient temperature in a sealed container, and a diluting agent comprising an organic liquid which is not a solvating agent; and
(2) HEC, an aqueous liquid, and a water soluble polar organic liquid which when uniformly mixed with HEC in a weight ratio of HEC to polar organic liquid of 1:2 produces a mixture with free liquid present after remaining quiescent for one week at ambient temperature in a sealed container. Preferably the aqueous liquid has a pH greater than 7.0.
Generally speaking, it has been found that virtually any organic compound which passes the solvation test described above, will function, to a usable degree, as a solvation agent. Non-limiting but preferred solvating agents include: aliphatic glycols containing from 2 to 5 carbon atoms such as ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,3-pentanediol and the like; alkylene triols containing from 2 to 6 carbon atoms such as glycerol, 1,2,3-butane-triol, 1,2,3-pentanetriol, and the like; amides containing from 1 to 4 carbon atoms such as formamide, acetamide, dimethyl formamide, and the like; and the mixtures of the various above compounds.
The diluting agent, in general, will be any liquid organic compound or material which is not a solvating agent. In general, the diluting agents are liquids which do not appreciably swell the HEC polymers, i.e. they do not produce semisolid or viscous mixtures which have no free liquid present after the one week solvation period described in the above test for determining solvating agents. Non-limiting examples of diluting agents include liquid aliphatic and aromatic hydrocarbons containing from 5 to 10 carbon atoms; kerosene, diesel oil, isopropanol, alkylene glycol ethers, vegetable oils, etc. Particularly preferred are organic liquids which are water soluble or miscible most preferably alkanols having at least 3 carbon atoms, ethylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and the like. The diluting agent will maintain the polymeric composition in a liquid, pourable state at a temperature of about 20° C. It will be understood, however, that lesser amounts of diluting agent can be used if desired and that the ultimate amount of diluting agent employed will depend upon the type of shear which is available to disperse the thickener. In general it has been found that desirable thickeners, which are pourable liquids, can be produced from compositions containing from about 10 to about 25% by weight HEC polymer, from about 2 to about 70% by weight diluting agent, and from about 5 to about 88% solvating agent.
HEC has been added to heavy brines to increase the viscosity of the brine such that the rate of loss of the brine to the formation contacted by the brine is reduced. Normally, in the absence of bridging particles, hydroxyethyl cellulose provides poor fluid loss control in those brines in which the HEC is fully hydrated. See for example co-pending patent application Ser. No. 161,444 filed June 20, 1980, entitled Thickened Heavy Brines, incorporated herein by reference.
We have found, as disclosed in co-pending patent application Ser. No. 161,444 filed June 20, 1980, that if the concentration of zinc bromide is less than about 20% by weight, the HEC will not efficiently gel or viscosify the brine. Indeed, we have found that while it is possible to viscosify a brine containing no zinc bromide or a brine solution containing a high concentration of zinc bromide, with HEC, if the two thickened solutions are admixed to produce a solution containing zinc bromide in less than about a 20% by weight concentration, the viscosity of the mixed brine will be essentially the same as if no HEC is present.
As indicated herein, it is a feature of this invention that HEC functions as an excellent fluid loss control additive in certain heavy brines in which the HEC is a very inefficient viscosifier. The HEC containing brines of this invention are cloudy or opaque as compared to the clear brines obtained when the HEC is completely, or nearly completely, hydrated. Apparently the HEC is not completely solubilized in these brines and thus at least a portion of the HEC is available to act as a bridging agent to decrease the fluid loss of these brines.
It is preferred in the practice of this invention that the HEC be activated such that the HEC will hydrate in these heavy brines at ambient temperature.
The concentration of HEC need only be sufficient to reduce the fluid loss of the brine. Preferably, the concentration of HEC will be from about 0.25 to about 5.0 ppb, more preferably, from about 0.25 to about 3.0 ppb.
It is another embodiment of this invention to provide a method of decreasing the fluid loss of heavy brines containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide, which comprises formulating the brine to contain from about 16% to about 20% by weight zinc bromide, and mixing with the brine a fluid loss reducing amount of HEC, as disclosed hereinbefore.
Still another embodiment of this invention provides a method of decreasing the fluid loss of heavy brines containing zinc bromide, calcium chloride, and calcium bromide, which comprises formulating the brine to contain greater than 20% zinc bromide and a concentration of calcium chloride of at least (2X-33)% by weight, where X is the % of zinc bromide, and mixing with the brine a fluid loss reducing amount of HEC, as disclosed hereinbefore.
To more fully illustrate the invention, the following nonlimiting examples are presented.
Heavy brines having the compositions listed in Table 1 were prepared by mixing together the indicated amounts of the following materials: a 19.2 ppg calcium bromide/zinc bromide solution containing 20% calcium bromide and 57% zinc bromide; a 14.2 ppg calcium bromide solution containing 53% calcium bromide; an 11.6 ppg calcium chloride solution containing 37.6% calcium chloride; and calcium chloride pellets containing 95% calcium chloride. After cooling to room temperature, there were added either: 3 ppb of NATROSOL 250 HHR hydroxyethyl cellulose; or 3 ppb of activated NATROSOL 250 HHR (i.e., 15 ppb of a composition containing 20% HEC, 25% glycerin, 54.6% isopropanol, and 0.4% CAB-O-SIL M5). Thereafter, the heavy brines were rolled 16 hours at room temperature and the API RP 13B rheology and fluid loss obtained. The heavy brines were then rolled 16 hours at 150oF, cooled at room temperature, and the API RP 13B data again obtained. The data obtained are given in Table 2.
The data indicate that heavy brines containing HEC can be formulated to exhibit a very low API fluid loss provided the % zinc bromide in the brine is in the range from about 16% to about 20% by weight, or the % zinc bromide is greater than 20% and the calcium chloride is greater than (2X-33)% where X is the % of zinc bromide in the brine. Preferably, the % zinc bromide is in the range from about 18% to about 20% and the % calcium chloride is less than about 5(X-17)%. In this preferred range the HEC solublizes to such an extent that appreciable viscosity is imparted to the heavy brine. The data also indicate that it is preferable to omit any solid calcium chloride from the heavy brine.
TABLE 1
__________________________________________________________________________
Brine Compositions
19.2
11.6
14.2
95%
Brine
Density
% % % ppg.
ppg.
ppg.
CaCl.sub.2
Number
ppg. ZnBr.sub.2
CaCl.sub.2
CaBr.sub.2
bbl.
bbl.
bbl.
lb.
__________________________________________________________________________
1 15.0 0 16.3
43.3
0 0.0285
0.8637
103
2 15.0 0 16.3
43.3
0 0.0285
0.8637
103
3 15.3 5.1 14.9
41.2
0.0714
0.0271
0.8014
95.7
4 15.3 5.1 14.9
41.2
0.0714
0.0271
0.8014
95.7
5 15.0 11.7
0 46.2
0.160
0 0.840
0
6 15.0 11.7
0 46.2
0.160
0 0.840
0
7 15.8 13.2
12.5
38.0
0.190
0.0229
0.700
83.4
8 15.8 13.2
12.5
38.0
0.190
0.0229
0.700
83.4
9 15.3 15.7
0 43.9
0.220
0 0.780
0
10 15.3 15.7
0 43.9
0.220
0 0.780
0
11 15.3 16.0
0 43.7
0.224
0 0.776
0
12 14.8 16.0
5.0 36.8
0.217
0.170
0.613
0
13 14.4 16.0
10.0
29.6
0.2105
0.330
0.4595
0
14 16.0 16.3
11.6
36.7
0.238
0.0214
0.658
78.5
15 16.0 16.3
11.6
36.7
0.238
0.0214
0.658
78.5
16 15.4 17.0
0 43.1
0.239
0 0.761
0
17 14.9 17.0
5.0 36.1
0.2317
0.171
0.5973
0
18 15.5 18.0
0 42.5
0.255
0 0.745
0
19 15.0 18.0
5.0 35.5
0.2465
0.172
0.5815
0
20 14.75
18.0
7.5 32.0
0.2427
0.2537
0.5036
0
21 14.5 18.0
10.0
28.5
0.239
0.334
0.427
0
22 15.5 18.4
0 42.4
0.260
0 0.740
0
23 15.5 18.4
0 42.4
0.260
0 0.740
0
24 15.5 19.0
0 42.1
0.270
0 0.730
0
25 15.1 19.0
5.0 34.8
0.2615
0.1735
0.565
0
26 14.6 19.0
10.0
28.0
0.2535
0.3335
0.413
0
27 14.25
19.0
14.0
22.3
0.2474
0.4573
0.2953
0
28 15.6 20.0
0 41.5
0.2855
0 0.7145
0
29 14.8 20.0
8.0 30.2
0.2714
0.2729
0.4557
0
30 14.8 20.0
8.0 30.2
0.2714
0.2729
0.4557
0
31 14.3 20.0
14.0
21.7
0.2614
0.460
0.2786
0
32 14.3 20.0
14.0
21.7
0.2614
0.460
0.2786
0
33 16.0 22.0
11.7
31.0
0.3214
0.120
0.4957
59.3
34 16.0 22.0
11.7
31.0
0.3214
0.120
0.4957
59.3
35 14.6 22.0
12.0
23.4
0.2943
0.4028
0.3029
0
36 14.6 22.0
12.0
23.4
0.2943
0.4028
0.3029
0
37 14.4 22.0
14.0
20.7
0.290
0.4628
0.2472
0
38 14.4 22.0
14.0
20.7
0.290
0.4628
0.2472
0
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
Brine Evaluation
3 ppb. NATROSOL 250 HHR.sup.(1)
16 Hours @ 74° F.
16 Hours @ 150° F.
API API
Brine
Rheology Fluid
API Rheology Fluid
Number
600 300 3 Loss.sup.(2)
600 300 3 Loss
__________________________________________________________________________
1 >300 >300 130
23 >300 >300 149 60
2 (68)
(35) (0)
(20)
(>300)
(>300)
(69)
(80)
3 56 29 2 125 67 34 1 NC
4 (62)
(31) (0)
(NC)
(60) (30) (1) (187)
5 15 8 0 NC 32 16 0 3
6 (14)
(7) (0)
(NC)
(16) (8) (0) (18)
7 51 26 0 131 63 32 2 NC
8 (49)
(25) (0)
NC) (51) (26) (0) (150)
9 24 12 0 NC 98 36 1 1
10 (15)
(7) (0)
(NC)
40 (24) (2) (4)
11 44 23 1 22 58 30 1 1
12 24 11 0 NC 33 15 0 4
13 21 11 0 NC 44 17 0 9.5
14 50 25 0 103 63 31 0 NC
15 (52)
(26) (0)
(NC)
(49) (25) (0) (120)
16 42 22 0 5 61 34 3 1
17 32 16 1 25 55 30 2 1
18 222 153 35 1 283 198 37 1
19 162 106 15 1 192 127 11 1
20 31 15 0 50 47 25 3 1
21 57 31 1 16 62 32 1 2
22 205 158 33 1 >300 184 44 1
23 (15)
(8) (1)
(NC)
(50) (25) (1) (2)
24 222 196 52 1 >300 227 59 1
25 193 161 39 1 274 198 46 1
26 158 104 12 1 187 120 10 1
27 41 21 0 4 52 28 1 1
28 202 218 57 1 >300 249 76 1
29 230 161 34 0 264 205 41 3
30 (14)
(8) (0)
(NC)
(63) (33) (1) (1)
31 152 101 9 1 >300 233 57 5
32 (14)
(7) (0)
(NC)
(48) (24) (1) (2)
33 46 23 1 29 172 101 5 1
34 (37)
(19) (0)
(NC)
(47) (24) (0) (2)
35 234 191 42 4 212 197 44 4
36 (16)
(8) (0)
(NC)
(103) (59) (1) (0.5)
37 229 170 39 2 213 140 11 5
38 (16)
(8) (0)
(NC)
(77) (41) (1) (0.2)
__________________________________________________________________________
.sup.(1) Data in parentheses obtained using dry, powdered NATROSOL 250 HH
.sup.(2) NC = No Control
The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalence of the claims are therefore intended to be embraced therein.
Claims (8)
1. A method of decreasing the fluid loss of heavy brines containing zinc bromide and at least one soluble salt selected from the group consisting of calcium chloride and calcium bromide, which comprises sequentially carrying out the steps of adjusting the concentration of zinc bromide in said brine to the range from about 16% to about 20% by weight, and mixing with said brine a fluid loss reducing amount of hydroxyethyl cellulose which has been activated by admixing said hydroxyethyl cellulose with an aqueous liquid having a pH of greater than 7 and a water-soluble polar organic liquid which when uniformly mixed with hydroxyethyl cellulose in a weight ratio of hydroxyethyl cellulose to polar organic liquid of 1:2 produces a mixture with free liquid present after remaining quiescent for one week at ambient temperature in a sealed container, said hydroxyethyl cellulose being incompletely solubilized in said brine whereby a portion of said hydroxyethyl cellulose acts as a bridging agent.
2. The method of claim 1 wherein said brine has a density in the range from about 14.2 to about 16.0 pounds per gallon.
3. The method of claim 2 wherein the concentration of hydroxyethyl cellulose is from about 0.25 to about 5.0 pounds per 42 gallon barrel.
4. The method of claim 2 wherein the concentration of hydroxyethyl cellulose is from about 0.25 to about 3.0 pounds per 42 gallon barrel.
5. A method of decreasing the fluid loss of heavy brine containing zinc bromide calcium chloride, and calcium bromide, which comprises adjusting the concentration of zinc bromide in said brine to greater than 20% by weight, adjusting the concentration of calcium chloride in said brine to at least (2X-33)% by weight, where X is the % by weight of zinc bromide, and mixing with said brine a fluid loss reducing amount of hydroxyethyl cellulose, the concentration of zinc bromide being adjusted prior to mixing said brine with said hydroxyethyl cellulose which has been activated by admixing said hydroxyethyl cellulose with an aqueous liuqid having a pH of greater than 7 and a water-soluble polar organic liquid which when uniformly mixed with hydroxyethyl cellulose in a weight ratio of hydroxyethyl cellulose to polar organic liquid of 1:2 produces a mixture with free liquid present after remaining quiescent for one week at ambient temperature in a sealed container, the concentration of zinc bromide being adjusted prior to mixing said brine with said hydroxyethyl cellulose, said hydroxyethyl cellulose being incompletely solubilized in said brine whereby a portion of said hydroxyethyl cellulose acts as a bridging agent.
6. The method of claim 5 wherein said brine has a density in the range from about 14.2 to about 16.0 pounds per gallon.
7. The method of claim 6 wherein the concentration of hydroxyethyl cellulose is from about 0.25 to about 5.0 pounds per 42 gallon barrel.
8. The method of claim 6 wherein the concentration of hydroxyethyl cellulose is from about 0.25 to about 3.0 pounds per 42 gallon barrel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/336,592 US5009798A (en) | 1980-06-20 | 1989-04-10 | Low fluid loss heavy brines containing hydroxyethyl cellulose |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/161,444 US4420406A (en) | 1980-06-20 | 1980-06-20 | Thickened heavy brines |
| US8020387A | 1987-07-29 | 1987-07-29 | |
| US07/336,592 US5009798A (en) | 1980-06-20 | 1989-04-10 | Low fluid loss heavy brines containing hydroxyethyl cellulose |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US8020387A Continuation | 1980-06-20 | 1987-07-29 |
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| Publication Number | Publication Date |
|---|---|
| US5009798A true US5009798A (en) | 1991-04-23 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/336,592 Expired - Fee Related US5009798A (en) | 1980-06-20 | 1989-04-10 | Low fluid loss heavy brines containing hydroxyethyl cellulose |
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| US5576271A (en) * | 1993-05-12 | 1996-11-19 | Phillips Petroleum Compay | Composition and process for stabilizing viscosity or controlling water loss of polymer-containing water based fluids |
| US20040216882A1 (en) * | 2002-09-12 | 2004-11-04 | M-I Llc | Remediation Treatment of Sustained Casing Pressures (SCP) In Wells with Top Down Surface Injection of Fluids and Additives |
| US20050274677A1 (en) * | 2004-06-09 | 2005-12-15 | Isaac D D | Methods for treating heavy halide brines with permanganates |
| US20100311621A1 (en) * | 2009-06-04 | 2010-12-09 | Rhodia Operations | Methods and compositions for viscosifying heavy aqueous brines |
| US20120157355A1 (en) * | 2010-12-17 | 2012-06-21 | Halliburton Energy Services, Inc. | Phosphate Based Blend for Drilling and Completion Fluid |
| US10377941B2 (en) | 2014-09-26 | 2019-08-13 | The Board Of Regents Of The University Of Oklahoma | Stabilized carbon nanotube suspensions |
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| US7244363B2 (en) | 2004-06-09 | 2007-07-17 | Halliburton Energy Services, Inc. | Methods for treating heavy halide brines with permanganates |
| US20100311621A1 (en) * | 2009-06-04 | 2010-12-09 | Rhodia Operations | Methods and compositions for viscosifying heavy aqueous brines |
| US9062238B2 (en) | 2009-06-04 | 2015-06-23 | Rhodia Operations | Methods and compositions for viscosifying heavy aqueous brines |
| US20120157355A1 (en) * | 2010-12-17 | 2012-06-21 | Halliburton Energy Services, Inc. | Phosphate Based Blend for Drilling and Completion Fluid |
| US9090807B2 (en) * | 2010-12-17 | 2015-07-28 | Halliburton Energy Services, Inc. | Phosphate based blend for drilling and completion fluid |
| US10377941B2 (en) | 2014-09-26 | 2019-08-13 | The Board Of Regents Of The University Of Oklahoma | Stabilized carbon nanotube suspensions |
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